US5525656A - Coating agents for coating aluminum - Google Patents
Coating agents for coating aluminum Download PDFInfo
- Publication number
- US5525656A US5525656A US08/285,770 US28577094A US5525656A US 5525656 A US5525656 A US 5525656A US 28577094 A US28577094 A US 28577094A US 5525656 A US5525656 A US 5525656A
- Authority
- US
- United States
- Prior art keywords
- parts
- weight
- tert
- vinyl ester
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000011248 coating agent Substances 0.000 title claims abstract description 34
- 238000000576 coating method Methods 0.000 title claims abstract description 18
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 230000009477 glass transition Effects 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- -1 saturated aliphatic monocarboxylic acids Chemical class 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 3
- 229920001519 homopolymer Polymers 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 56
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 36
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 28
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 27
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 24
- 239000001530 fumaric acid Substances 0.000 claims description 14
- FNMTVMWFISHPEV-AATRIKPKSA-N dipropan-2-yl (e)-but-2-enedioate Chemical compound CC(C)OC(=O)\C=C\C(=O)OC(C)C FNMTVMWFISHPEV-AATRIKPKSA-N 0.000 claims description 13
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims description 12
- FNMTVMWFISHPEV-WAYWQWQTSA-N dipropan-2-yl (z)-but-2-enedioate Chemical compound CC(C)OC(=O)\C=C/C(=O)OC(C)C FNMTVMWFISHPEV-WAYWQWQTSA-N 0.000 claims description 11
- MSVGHYYKWDQHFV-BQYQJAHWSA-N ditert-butyl (e)-but-2-enedioate Chemical compound CC(C)(C)OC(=O)\C=C\C(=O)OC(C)(C)C MSVGHYYKWDQHFV-BQYQJAHWSA-N 0.000 claims description 11
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 11
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- MSVGHYYKWDQHFV-FPLPWBNLSA-N ditert-butyl (z)-but-2-enedioate Chemical compound CC(C)(C)OC(=O)\C=C/C(=O)OC(C)(C)C MSVGHYYKWDQHFV-FPLPWBNLSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 10
- 239000011976 maleic acid Substances 0.000 claims description 10
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 10
- LAIJAUHBAWLPCO-UHFFFAOYSA-N (4-tert-butylcyclohexyl) prop-2-enoate Chemical compound CC(C)(C)C1CCC(OC(=O)C=C)CC1 LAIJAUHBAWLPCO-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 8
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 claims description 6
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 4
- WUMMIJWEUDHZCL-UHFFFAOYSA-N 3-prop-2-enyloxolane-2,5-dione Chemical compound C=CCC1CC(=O)OC1=O WUMMIJWEUDHZCL-UHFFFAOYSA-N 0.000 claims description 4
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 4
- 229940018557 citraconic acid Drugs 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 claims description 4
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 3
- 229920006395 saturated elastomer Polymers 0.000 claims 3
- ZAHZTYCUJPVCCK-UHFFFAOYSA-N (4,4-ditert-butylcyclohexyl) prop-2-enoate Chemical compound C(C=C)(=O)OC1CCC(CC1)(C(C)(C)C)C(C)(C)C ZAHZTYCUJPVCCK-UHFFFAOYSA-N 0.000 claims 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims 1
- 239000008199 coating composition Substances 0.000 abstract description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 abstract description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 104
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 82
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 81
- 229910052757 nitrogen Inorganic materials 0.000 description 52
- 238000011010 flushing procedure Methods 0.000 description 51
- 239000000243 solution Substances 0.000 description 34
- 238000006116 polymerization reaction Methods 0.000 description 29
- 239000011888 foil Substances 0.000 description 26
- 230000035484 reaction time Effects 0.000 description 25
- 238000010992 reflux Methods 0.000 description 22
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 21
- 238000007789 sealing Methods 0.000 description 18
- 239000011324 bead Substances 0.000 description 17
- 238000001816 cooling Methods 0.000 description 17
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 description 16
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 16
- 235000019400 benzoyl peroxide Nutrition 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 13
- 239000003999 initiator Substances 0.000 description 11
- 229920006254 polymer film Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 6
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 229940059864 chlorine containing product ectoparasiticides Drugs 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- ZGPBOPXFOJBLIV-UHFFFAOYSA-N butoxycarbonyloxy butyl carbonate Chemical compound CCCCOC(=O)OOC(=O)OCCCC ZGPBOPXFOJBLIV-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QWVBGCWRHHXMRM-UHFFFAOYSA-N hexadecoxycarbonyloxy hexadecyl carbonate Chemical compound CCCCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCCCC QWVBGCWRHHXMRM-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012945 sealing adhesive Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- 150000003513 tertiary aromatic amines Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
Definitions
- the invention relates to a coating agent composition for coating aluminum which is based on vinyl ester copolymers.
- packaging materials also include aluminum foil to a large extent. This can be used by itself or in combination with other substances, such as plastics (PE, PP, PS, PVC, PET and the like, glass or cardboard.
- PET plastics
- the heat-sealing method is used, which means that the materials are firmly bonded to one another by applying elevated temperature and pressure.
- untreated aluminum foil is not sealable, it is coated with a polymer film, a heat-sealing coating or else a heat-sealing adhesive.
- a heat-sealing coating should, therefore, have a good adhesion to aluminum foil and should be transparent; it should be possible to paint over it, it should be readily sealable with itself and other materials, storage-stable and physiologically acceptable, and it should have a glass transition temperature of not more than 100° C. and at the same time the highest possible block point in order to avoid sticking of the coated aluminum foil.
- Polyacrylates or polymethacrylates such as are described in EP-A1 417 570 (CA-A 2025368) or EP-A2 316 753, and chlorine-containing polymers such as are known from DE-C2 29 06 118 (U.S. Pat. No. 4,267,094) are employed as heat-sealing coatings for coating aluminum foil.
- a disadvantage of the polyacrylates and polymethacrylates is their generally poor adhesion to aluminum. When these polymers are used, the aluminum foil must be primed beforehand in most cases. Chlorine-containing copolymers are as a rule employed as primers, so that chlorine-containing products, either by themselves or in combination with acrylate systems, are currently used in most cases for laminating aluminum foil.
- the object of providing a coating agent composition specifically for finishing aluminum foil which neither comprises chlorine-containing polymers nor has to be applied using a chlorine-containing primer.
- the polymers on which the coating agent is based should therefore have both a good adhesion to aluminum and a good sealing seam strength, in the dry and in the wet state, for use as a heat-sealing coating.
- the invention relates to a coating agent composition for coating aluminum which is based on vinyl ester copolymers and an organic solvent, the vinyl ester copolymer comprising
- Vinyl acetate or vinyl propionate is preferably employed as component A), in particular, the monomer component A) comprises vinyl acetate.
- component B comprises VeoVa 9.
- the copolymer preferably comprises, as component C), crotonic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, allylsuccinic anhydride, mesaconic acid, citraconic acid and/or citraconic anhydride.
- Maleic anhydride and fumaric acid are particularly preferred.
- Methyl methacrylate, tert-butyl acrylate, N-vinylpyrrolidone, N-vinylcarbazole, dimethyl maleate, diisopropyl maleate, diisopropyl fumarate, di-tert-butyl maleate, di-tert-butyl fumarate and 4-tert-butylcyclohexyl acrylate are preferably employed as component D).
- Diisopropyl fumarate and di-tert-butyl fumarate are particularly preferred.
- the vinyl ester copolymers have a glass transition temperature T 8 of 20° to 100° C., a block point in the range from 30° to 150° C. and a K value of 25 to 120, and comprise:
- one or more comonomers from the group comprising methyl methacrylate, tert-butyl acrylate, N-vinylpyrrolidone, N-vinylcarbazole, dimethyl maleate, diisopropyl maleate, diisopropyl fumarate, di-tert-butyl maleate, di-tert-butyl fumarate and 4-tert-butylcyclohexyl acrylate.
- Vinyl ester copolymers which have a glass transition temperature T 8 of 30° to 70° C., a block point in the range from 45° to 100° C. and a K value of 30 to 80 and which comprise
- one or more comonomers from the group comprising methyl methacrylate, tert-butyl acrylate, N-vinylpyrrolidone, N-vinylcarbazole, dimethyl maleate, diisopropyl maleate, diisopropyl fumarate, di-tert-butyl maleate, di-tert-butyl fumarate and 4-tert-butylcyclohexyl acrylate.
- Vinyl ester copolymers which have a glass transition temperature T 8 of 30° to 70° C., a block point in the range from 45° to 100° C. and a K value of 30 to 80 and which comprise
- Vinyl ester copolymers which have a glass transition temperature T g of 30° to 70° C., a block point in the range from 45° to 100° C. and a K value of 30 to 80 and which comprise
- Vinyl ester copolymers which are most preferred are those which have a glass transition temperature T g of 30° to 70° C., a block point in the range from 45° to 100° C. and a K value of 30 to 80 and which comprise
- Vinyl ester copolymers which comprise A) 60 to 85 parts by weight of vinyl acetate, C) 0.5 to 3 parts by weight of fumaric acid and/or maleic anhydride and D) 15 to 40 parts by weight of one or more comonomers from the group comprising dimethyl maleate, diisopropyl maleate, diisopropyl fumarate, di-tert-butyl maleate and di-tert-butyl fumarate, are not known in the prior art.
- the vinyl ester copolymers can be prepared by free radical polymerization in an organic solvent, such as, for example, ethyl acetate, acetone or tert-butanol, in emulsion with the addition of customary emulsifiers and protective colloids, or in suspension with the aid of protective colloids.
- an organic solvent such as, for example, ethyl acetate, acetone or tert-butanol
- the suspension polymerization process is preferably used.
- Alkyl sulfates, alkylsulfonates, ethoxylated alcohols and sulfated products thereof have proven to be suitable emulsifiers for the emulsion polymerization.
- Protective colloids which can be employed successfully in the suspension polymerization are, inter alia, polyvinylpyrrolidone, polyvinyl alcohol, cellulose derivatives, such as hydroxyethyl cellulose, vinyl ester copolymers containing carboxylic acid and also inorganic dispersing agents, such as aluminum hydroxide or magnesium hydroxide.
- Both the emulsion and the suspension polymerization can be carried out by the initial mixture process or by the feed process, it being possible for the composition of the feed to be the same as or different from that of any initial mixture present.
- Initiators which can be used for the polymerization are, for the emulsion polymerization, the customary water-soluble agents which form free radicals, such as sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate and tert-butyl hydroperoxide, and, for the suspension and solution polymerization, the customary organic peroxides and azo compounds, such as dibutyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, bis(2-ethylhexyl) peroxydicarbonate, dicetyl peroxydicarbonate, tert-butyl peroxypivalate, dilauryl peroxide, dibenzoyl peroxide, dicumyl peroxide, tert-butyl peroxy-2-ethylhexanoate, 2,2-bis(tert-butylperoxy)butane, ter
- One initiator by itself or a mixture of various initiators can be used for the polymerization.
- For the suspension polymerization it has proved appropriate to use a combination of initiators having different decomposition temperatures (different half-lives at the given polymerization temperature), since a faster and more continuous polymerization reaction is achieved in this way.
- the initiator or initiators as a rule are also introduced with the initial mixture for the suspension polymerization, since the organic initiators used diffuse only with difficulty into the beads via the aqueous phase, it is in general more appropriate in the case of the emulsion polymerization and the polymerization in an organic solvent for only some of the initiator or initiators to be initially introduced and for the remainder to be metered in over the course of the reaction.
- reducing compounds such as bisulfite, dithionite, Rongalit or tertiary aromatic amines, or ascorbic acid
- the initiators are as a rule employed in amounts between 0.01.and 1.0 % by weight, based on the sum of the monomers.
- the polymerization temperature is between 30° and 95° C., depending on whether a purely thermal or a redox system is used. Toward the end of the polymerization, the temperature is in general brought to a temperature higher than the initial polymerization temperature in order to bring the reaction to completion.
- the vinyl ester copolymers are isolated in the customary manner. In the case of suspension polymers, isolation is carried out by filtration with suction, washing with water and subsequent drying. If the polymerization is carried out in an organic solvent, the copolymer can be isolated by precipitating in a precipitant, such as, for example, methanol or petroleum benzine, in which case the volume ratio of precipitant to solution should be at least 5:1. The polymer can also be isolated by distilling off the solvent.
- the emulsion polymers can be isolated by casting a film or by coagulation of the emulsion by means of polyvalent metal salts or freezing.
- the vinyl ester copolymers are dissolved in an organic solvent for formulation of the heat-sealing coating compositions according to the invention.
- Suitable solvents are carboxylic acid esters, such as ethyl acetate; ketones, such as acetone and methyl ethyl ketone; alcohols, such as ethanol, propanol and butanol; ethers, such as tetrahydrofuran; and chlorinated hydrocarbons, such as methylene chloride and chloroform.
- Acetone or ethyl acetate is preferably used as the solvent.
- the solids content of the solutions is in the range from 10 to 70, preferably 20 to 40, % by weight.
- the coating agent composition according to the invention is applied, for example, by spraying, dipping, brushing, pouring or knife-coating or in another suitable manner.
- the amount applied here is usually chosen such that a layer of 5 to 50 ⁇ m results after drying.
- the coated substrate is dried at elevated temperature, if appropriate under reduced pressure.
- the coating agents according to the invention which are based on vinyl ester copolymers are suitable above all for providing aluminum with a heat-sealing coating and as a primer for the heat-sealing coating. They exhibit good adhesion even to untreated aluminum foil.
- the coating is transparent and has a high flexibility at room temperature.
- the sealing seam strengths of the polymers here surprisingly depend on the preparation method: the strength is generally highest for the polymers prepared by the suspension polymerization process and lowest for the products synthesized in an organic solvent.
- the following examples serve to further illustrate the invention.
- the examples relate to the preparation of the vinyl ester copolymers on which the compositions according to the invention are based and to the preparation of the coating agent solutions.
- the heat-sealing coating compositions prepared in the examples were subjected to technological testing by the methods described below, the results of which are listed in Table 1.
- the mixture was heated to 70° C., while flushing vigorously with nitrogen. After a reaction time of 6 hours, a water pump vacuum was applied at a temperature of 80° C. for one hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large amount of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
- Eballoid is a polyvinyl ester containing carboxyl groups, a product from Wacker Chemie GmbH
- Eballoid is a polyvinyl ester containing carboxyl groups, a product from Wacker Chemie GmbH
- the K values were determined in tetrahydrofuran in accordance with H. Fikentscher, Cellulosechemie 13, 58-64 (1932).
- the glass transition temperatures were determined by means of DSC measurements using an apparatus from Perkin Elmer, the middle point of the glass stage being taken as the glass transition temperature and the heating rate being in each case 20° C./minute.
- the foil was first cleaned with ethanol and then coated with a 50 ⁇ m wet film (20%) and dried at 120° C. for 20 minutes. A strip of tesafilm adhesive tape was pressed onto this polymer film with firm finger pressure. The adhesive strip was in one case torn off again immediately; the second test was carried out after the coated aluminum foil had been stored in water at room temperature for 24 hours. The film was then wiped dry with a cloth and the tesa strip was stuck on with firm finger pressure and immediately torn off again. The third test was carried out after the coated aluminum foil had been stored in water for 24 hours and then stored at room temperature for 24 hours. Thereafter, the adhesive strip was fixed with firm finger pressure and immediately torn off again. The adhesive strength was evaluated visually in accordance with the following scale of ratings:
- the aluminum foil was coated with a 50 ⁇ m wet film (20% strength) and dried at 120° C. for 20 minutes. Thereafter, the aluminum foil was folded so that the coated areas lay on top of one another. Testing was carried out in a sealing unit at various temperatures to ascertain whether the polymer films stick together, the sealing time being 30 seconds and the pressing pressure 2.5 Kp/cm 2 . The temperature in °C. at which the aluminum foil can no longer be separated without applying force, that is to say the polymer film became tacky, was stated as the block point or block temperature.
- the sealing seam strength was determined by the following method: an aluminum foil coated with a 50 ⁇ m wet film (20% strength) and dried at 120° C. for 20 minutes was folded together so that the sides coated with the polymer lay on top of one another.
- the foil was sealed with a sealing unit at a temperature of 190° C. for 0.5 second under a pressing pressure of 10 Kp/cm 2 .
- the sealing area was 4 ⁇ 1 cm.
- the force required to peel the aluminum foil apart again at room temperature was then measured on a unit from Instron. The measurement was carried out both in the dry and in the wet state.
- the coated and sealed aluminum foil was first stored in water at room temperature for 24 hours and then examined immediately as described above.
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Abstract
The invention provides a coating composition for coating aluminum which is based on vinyl ester copolymers and an organic solvent, the vinyl ester copolymer comprising
a) 20 to 90 parts by weight of a vinyl ester of saturated aliphatic monocarboxylic acids having 1 to 5 C atoms,
b) 0 to 70 parts by weight of a vinyl ester of saturated aliphatic monocarboxylic acids which have 9 to 10 C atoms and a quaternary C atom in the α-position relative to the carboxyl group,
c) 0.05 to 10 parts by weight of one or more ethylenically unsaturated mono- or dicarboxylic acids having 3 to 10 C atoms or anhydrides thereof and
d) 0 to 50 parts by weight of one or more ethylenically unsaturated monomers, the homopolymers of which have a glass transition temperature above 30° C.
The coating composition is free of chlorine-containing polymers and also avoids the necessity for using a chlorine-containing primer.
Description
This application is a continuation of application Ser. No. 08/072,712, filed Jun. 7, 1993, now abandoned.
1) Field of the Invention
The invention relates to a coating agent composition for coating aluminum which is based on vinyl ester copolymers.
2 ) Background Art
Many things in daily life, especially in the foodstuffs, cosmetics and medicines sector, are packaged with flexible materials. These packaging materials also include aluminum foil to a large extent. This can be used by itself or in combination with other substances, such as plastics (PE, PP, PS, PVC, PET and the like, glass or cardboard. To seal the materials mentioned with the aluminum foil, for example, the heat-sealing method is used, which means that the materials are firmly bonded to one another by applying elevated temperature and pressure. However, since untreated aluminum foil is not sealable, it is coated with a polymer film, a heat-sealing coating or else a heat-sealing adhesive. During the sealing operation, the polymer becomes soft due to the elevated temperature and, in conjunction with the pressing pressure applied, ensures, in the cooled state, bonding of the materials to be sealed. A heat-sealing coating should, therefore, have a good adhesion to aluminum foil and should be transparent; it should be possible to paint over it, it should be readily sealable with itself and other materials, storage-stable and physiologically acceptable, and it should have a glass transition temperature of not more than 100° C. and at the same time the highest possible block point in order to avoid sticking of the coated aluminum foil.
Polyacrylates or polymethacrylates such as are described in EP-A1 417 570 (CA-A 2025368) or EP-A2 316 753, and chlorine-containing polymers such as are known from DE-C2 29 06 118 (U.S. Pat. No. 4,267,094) are employed as heat-sealing coatings for coating aluminum foil. A disadvantage of the polyacrylates and polymethacrylates is their generally poor adhesion to aluminum. When these polymers are used, the aluminum foil must be primed beforehand in most cases. Chlorine-containing copolymers are as a rule employed as primers, so that chlorine-containing products, either by themselves or in combination with acrylate systems, are currently used in most cases for laminating aluminum foil. Vinyl chloride/vinyl acetate/vinyl alcohol tarpolymers (DE-OS 28 38 383=U.S. Pat. No. 4,141,870) and vinyl chloride graft copolymers (EP-A-117 350) are known from the literature for coating aluminum. Recently, however, the use of chlorine-containing products in short-lived packaging material, above all in the foodstuffs sector, has been avoided as far as possible. There is accordingly an urgent need for chlorine-free polymers for coating aluminum, specifically for finishing aluminum foil.
There was, then, the object of providing a coating agent composition specifically for finishing aluminum foil, which neither comprises chlorine-containing polymers nor has to be applied using a chlorine-containing primer. The polymers on which the coating agent is based should therefore have both a good adhesion to aluminum and a good sealing seam strength, in the dry and in the wet state, for use as a heat-sealing coating.
The invention relates to a coating agent composition for coating aluminum which is based on vinyl ester copolymers and an organic solvent, the vinyl ester copolymer comprising
A) 20 to 90 parts by weight of a vinyl ester of saturated aliphatic monocarboxylic acids having 1 to 5 C atoms,
B) 0 to 70 parts by weight of a vinyl ester of saturated aliphatic monocarboxylic acids which have 9 to 10 C atoms and a quaternary C atom in the α-position relative to the carboxyl group,
C) 0.05 to 10 parts by weight of one or more ethylenically unsaturated mono- or dicarboxylic acids having 3 to 10 C atoms or anhydrides thereof and
D) 0 to 50 parts by weight of one or more ethylenically unsaturated monomers, the homopolymers of which have a glass transition temperature above 30° C.
Vinyl acetate or vinyl propionate is preferably employed as component A), in particular, the monomer component A) comprises vinyl acetate.
The Versatic acid vinyl ester mixtures VeoVa 9 and VeoVa 10 (commercial products from Shell Chemie GmbH) or individual constituents of these mixtures are preferred as component B). In particular, component B) comprises VeoVa 9.
The copolymer preferably comprises, as component C), crotonic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, allylsuccinic anhydride, mesaconic acid, citraconic acid and/or citraconic anhydride. Maleic anhydride and fumaric acid are particularly preferred.
Methyl methacrylate, tert-butyl acrylate, N-vinylpyrrolidone, N-vinylcarbazole, dimethyl maleate, diisopropyl maleate, diisopropyl fumarate, di-tert-butyl maleate, di-tert-butyl fumarate and 4-tert-butylcyclohexyl acrylate are preferably employed as component D). Diisopropyl fumarate and di-tert-butyl fumarate are particularly preferred.
In a preferred embodiment, the vinyl ester copolymers have a glass transition temperature T8 of 20° to 100° C., a block point in the range from 30° to 150° C. and a K value of 25 to 120, and comprise:
A) 25 to 85 parts by weight of vinyl acetate,
B) 0 to 55 parts by weight of VeoVa 9,
C) 0.5 to 5 parts by weight of one or more comonomers from the group comprising crotonic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, allylsuccinic anhydride, mesaconic acid, citraconic acid and citraconic anhydride and
D) 0 to 40 parts by weight of one or more comonomers from the group comprising methyl methacrylate, tert-butyl acrylate, N-vinylpyrrolidone, N-vinylcarbazole, dimethyl maleate, diisopropyl maleate, diisopropyl fumarate, di-tert-butyl maleate, di-tert-butyl fumarate and 4-tert-butylcyclohexyl acrylate.
The following vinyl ester copolymers are particularly preferred:
Vinyl ester copolymers which have a glass transition temperature T8 of 30° to 70° C., a block point in the range from 45° to 100° C. and a K value of 30 to 80 and which comprise
A) 40 to 50 parts by weight of vinyl acetate,
B) 40 to 50 parts by weight of VeoVa 9,
C) 0.5 to 3 parts by weight of one or more comonomers from the group comprising crotonic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and maleic anhydride and
D) 5 to 20 parts by weight of one or more comonomers from the group comprising methyl methacrylate, tert-butyl acrylate, N-vinylpyrrolidone, N-vinylcarbazole, dimethyl maleate, diisopropyl maleate, diisopropyl fumarate, di-tert-butyl maleate, di-tert-butyl fumarate and 4-tert-butylcyclohexyl acrylate.
Vinyl ester copolymers which have a glass transition temperature T8 of 30° to 70° C., a block point in the range from 45° to 100° C. and a K value of 30 to 80 and which comprise
A) 45 to 55 parts by weight of vinyl acetate,
B) 45 to 55 parts by weight of VeoVa 9 and
C) 0.5 to 3 parts by weight of one or more comonomers from the group comprising crotonic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and maleic anhydride.
Vinyl ester copolymers which have a glass transition temperature Tg of 30° to 70° C., a block point in the range from 45° to 100° C. and a K value of 30 to 80 and which comprise
A) 60 to 85 parts by weight of vinyl acetate,
C) 0.5 to 3 parts by weight of one or more comonomers from the group comprising crotonic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and maleic anhydride and
D) 15 to 40 parts by weight of one or more comonomers from the group comprising dimethyl maleate, diisopropyl maleate, diisopropyl fumarate, di-tert-butyl maleate, di-tert-butyl fumarate and 4-tert-butylcyclohexyl acrylate.
Vinyl ester copolymers which are most preferred are those which have a glass transition temperature Tg of 30° to 70° C., a block point in the range from 45° to 100° C. and a K value of 30 to 80 and which comprise
A) 60 to 85 parts by weight of vinyl acetate,
C) 0.5 to 3 parts by weight of fumaric acid and/or maleic anhydride and
D) 15 to 40 parts by weight of one or more comonomers from the group comprising dimethyl maleate, diisopropyl maleate, diisopropyl fumarate, di-tert-butyl maleate, di-tert-butyl fumarate and 4-tert-butylcyclohexyl acrylate.
Vinyl ester copolymers which comprise A) 60 to 85 parts by weight of vinyl acetate, C) 0.5 to 3 parts by weight of fumaric acid and/or maleic anhydride and D) 15 to 40 parts by weight of one or more comonomers from the group comprising dimethyl maleate, diisopropyl maleate, diisopropyl fumarate, di-tert-butyl maleate and di-tert-butyl fumarate, are not known in the prior art.
The vinyl ester copolymers can be prepared by free radical polymerization in an organic solvent, such as, for example, ethyl acetate, acetone or tert-butanol, in emulsion with the addition of customary emulsifiers and protective colloids, or in suspension with the aid of protective colloids. The suspension polymerization process is preferably used.
Alkyl sulfates, alkylsulfonates, ethoxylated alcohols and sulfated products thereof have proven to be suitable emulsifiers for the emulsion polymerization. Protective colloids which can be employed successfully in the suspension polymerization are, inter alia, polyvinylpyrrolidone, polyvinyl alcohol, cellulose derivatives, such as hydroxyethyl cellulose, vinyl ester copolymers containing carboxylic acid and also inorganic dispersing agents, such as aluminum hydroxide or magnesium hydroxide.
Both the emulsion and the suspension polymerization can be carried out by the initial mixture process or by the feed process, it being possible for the composition of the feed to be the same as or different from that of any initial mixture present.
Initiators which can be used for the polymerization are, for the emulsion polymerization, the customary water-soluble agents which form free radicals, such as sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate and tert-butyl hydroperoxide, and, for the suspension and solution polymerization, the customary organic peroxides and azo compounds, such as dibutyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, bis(2-ethylhexyl) peroxydicarbonate, dicetyl peroxydicarbonate, tert-butyl peroxypivalate, dilauryl peroxide, dibenzoyl peroxide, dicumyl peroxide, tert-butyl peroxy-2-ethylhexanoate, 2,2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, dicyclohexyl peroxydicarbonate and 2,2'-azoisobutyronitrile.
One initiator by itself or a mixture of various initiators can be used for the polymerization. For the suspension polymerization, it has proved appropriate to use a combination of initiators having different decomposition temperatures (different half-lives at the given polymerization temperature), since a faster and more continuous polymerization reaction is achieved in this way. While the initiator or initiators as a rule are also introduced with the initial mixture for the suspension polymerization, since the organic initiators used diffuse only with difficulty into the beads via the aqueous phase, it is in general more appropriate in the case of the emulsion polymerization and the polymerization in an organic solvent for only some of the initiator or initiators to be initially introduced and for the remainder to be metered in over the course of the reaction. Furthermore, it is often advantageous also to add reducing compounds, such as bisulfite, dithionite, Rongalit or tertiary aromatic amines, or ascorbic acid, in addition to the initiators. The initiators are as a rule employed in amounts between 0.01.and 1.0 % by weight, based on the sum of the monomers. The polymerization temperature is between 30° and 95° C., depending on whether a purely thermal or a redox system is used. Toward the end of the polymerization, the temperature is in general brought to a temperature higher than the initial polymerization temperature in order to bring the reaction to completion.
The vinyl ester copolymers are isolated in the customary manner. In the case of suspension polymers, isolation is carried out by filtration with suction, washing with water and subsequent drying. If the polymerization is carried out in an organic solvent, the copolymer can be isolated by precipitating in a precipitant, such as, for example, methanol or petroleum benzine, in which case the volume ratio of precipitant to solution should be at least 5:1. The polymer can also be isolated by distilling off the solvent. The emulsion polymers can be isolated by casting a film or by coagulation of the emulsion by means of polyvalent metal salts or freezing.
The vinyl ester copolymers are dissolved in an organic solvent for formulation of the heat-sealing coating compositions according to the invention. Suitable solvents are carboxylic acid esters, such as ethyl acetate; ketones, such as acetone and methyl ethyl ketone; alcohols, such as ethanol, propanol and butanol; ethers, such as tetrahydrofuran; and chlorinated hydrocarbons, such as methylene chloride and chloroform. Acetone or ethyl acetate is preferably used as the solvent. The solids content of the solutions is in the range from 10 to 70, preferably 20 to 40, % by weight.
For coating aluminum foils, for example, the coating agent composition according to the invention is applied, for example, by spraying, dipping, brushing, pouring or knife-coating or in another suitable manner. The amount applied here is usually chosen such that a layer of 5 to 50 μm results after drying. Finally, the coated substrate is dried at elevated temperature, if appropriate under reduced pressure.
The coating agents according to the invention which are based on vinyl ester copolymers are suitable above all for providing aluminum with a heat-sealing coating and as a primer for the heat-sealing coating. They exhibit good adhesion even to untreated aluminum foil. The coating is transparent and has a high flexibility at room temperature. The sealing seam strengths of the polymers here surprisingly depend on the preparation method: the strength is generally highest for the polymers prepared by the suspension polymerization process and lowest for the products synthesized in an organic solvent.
The following examples serve to further illustrate the invention. The examples relate to the preparation of the vinyl ester copolymers on which the compositions according to the invention are based and to the preparation of the coating agent solutions. The heat-sealing coating compositions prepared in the examples were subjected to technological testing by the methods described below, the results of which are listed in Table 1.
42 parts of vinyl acetate, 42 parts of VeoVa 9, 15 parts of tert-butyl acrylate, 1 part of maleic anhydride, 0.1 part of bis(2-ethylhexyl) peroxodicarbonate, 0.1 part of tert-butyl peroxypivalate and 0.05 part of dibenzoyl peroxide were initially introduced into a polymerization vessel with an anchor stirrer, reflux condenser and nitrogen flushing device, and the mixture was diluted with ethyl acetate such that a 40% strength solution was formed. It was then heated up, while flushing vigorously with nitrogen, and kept under reflux for 12 hours. Thereafter, a water pump vacuum was applied for 2 hours and the mixture was cooled to room temperature. The solids content was 65% and was adjusted to 20% with ethyl acetate.
6 parts of vinyl acetate, 6 parts of VeoVa 9, 12.5 parts of tert-butyl acrylate, 1 part of maleic anhydride, 1.5 parts of polyvinyl alcohol (hydrolysis number 140, Hoppler viscosity of a 4% strength solution 5), 1 part of Genapol X 360 (emulsifier from Hoechst), 0.2 part of sodium bicarbonate and 99 parts of water were initially introduced into a polymerization vessel with an anchor stirrer, reflux condenser, nitrogen flushing device and metering device. While being heated up to 70° C., the mixture was flushed intensively with nitrogen. When the stated temperature had been reached, 0.1 part of potassium peroxodisulfate in 6 parts of water was added. After the reaction had started, the following three meterings were effected over a period of 2 hours. Metering 1:0.2 part of potassium peroxodisulfate in 12 parts of water. Metering 2:36.5 parts of tert-butyl acrylate, 19 parts of VeoVa 9 and 19 parts of vinyl acetate. Metering 3:0.4 part of sodium bicarbonate and 3 parts of Genapol X 360 in 18 parts of water. After a reaction time of 5 hours, the internal temperature was increased to 80° C. and a water pump vacuum was applied for 1 hour. After the mixture had been cooled to room temperature, a perfect dispersion having a solids content of 40% resulted. The dispersion was coagulated at -18° C., the coagulate was filtered off, washed with a large quantity of water and dried and a 20% strength solution of the solid resin in ethyl acetate was prepared.
49 parts of vinyl acetate, 50 parts of VeoVa 9, 1 part of maleic acid, 0.05 part of tert-butyl peroxypivalate and 5 parts of polyvinylpyrrolidone K 30 (product from GAF) were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser and nitrogen flushing device, and water was added, while stirring, in an amount such that the content of monomers was 35 percent by weight. The mixture was heated to 70 ° C., while flushing vigorously with nitrogen. After a reaction time of 6 hours, a water pump vacuum was applied for one hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large quantity of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
49 parts of vinyl acetate, 50 parts of VeoVa 9, 1 part of itaconic acid, 0.05 part of tert-butyl peroxypivalate and 5 parts of polyvinylpyrrolidone K 30 (product from GAY) were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser and nitrogen flushing device, and water was added, while stirring, in an amount such that the content of monomers was 35 percent by weight. The mixture was heated to 70° C., while flushing vigorously with nitrogen. After a reaction time of 6 hours, a water pump vacuum was applied for one hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large quantity of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
49 parts of vinyl acetate, 50 parts of VeoVa 9, 1 part of maleic anhydride, 0.05 part of tert-butyl peroxypivalate and 5 parts of polyvinylpyrrolidone K 30 (product from GAY) were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser and nitrogen flushing device, and water was added, while stirring, in an amount such that the content of monomers was 35 percent by weight. The mixture was heated to 70° C., while flushing vigorously with nitrogen. After a reaction time of 6 hours, a water pump vacuum was applied for one hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large quantity of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
139 parts of water and 2 parts of polyvinylpyrrolidone K 90 as a 5% strength solution in water (a product from GAF) were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser, metering device and nitrogen flushing device, and the mixture was heated to 70° C., while flushing with nitrogen. When the temperature had been reached, the following meterings were carried out, while stirring vigorously and flushing with nitrogen: Metering 1: a mixture of 49 parts of vinyl acetate, 50 parts of VeoVa 9, 1 part of allylsuccinic anhydride, 0.1 part of tert-butyl peroxypivalate and 0.05 part of dibenzoyl peroxide. Metering 2: 6 parts of water and 0.1 part of bis(2-ethylhexyl) peroxodicarbonate. After a reaction time of 3 hours, the temperature was increased to 83° C., and after a reaction time of a further two hours, a water pump vacuum was applied for one hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large quantity of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
139 parts of water and 2 parts of polyvinylpyrrolidone K 90 as a 5% strength solution in water (a product from GAF) were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser, metering device and nitrogen flushing device, and the mixture was heated to 70° C., while flushing with nitrogen. When the temperature had been reached, the following meterings were rapidly carried out, while stirring vigorously and flushing with nitrogen: Metering 1: a mixture of 49 parts of vinyl acetate, 49 parts of VeoVa 9, 2 parts of mesaconic acid, 0.1 part of tert-butyl peroxypivalate and 0.05 part of dibenzoyl peroxide. Metering 2: 6 parts of water and 0.1 part of bis(2-ethylhexyl) peroxodicarbonate. After a reaction time of 4 hours, the temperature was increased to 80° C., and after a reaction time of a further two hours, a water pump vacuum was applied for one hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large quantity of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
139 parts of water and 2 parts of polyvinylpyrrolidone K 90 in a 5% strength solution in water (a product from GAF) were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser, metering device and nitrogen flushing device, and the mixture was heated to 70° C., while flushing with nitrogen. When the temperature had been reached, the following meterings were rapidly carried out, while stirring vigorously and flushing with nitrogen: Metering 1: a mixture of 49 parts of vinyl acetate, 50 parts of VeoVa 9, 1 part of citraconic acid, 0.1 part of tert-butyl peroxypivalate and 0.05 part of dibenzoyl peroxide. Metering 2: 6 parts of water and 0.1 part of bis(2-ethylhexyl) peroxodicarbonate. After a reaction time of 4 hours, the temperature was increased to 80° C., and after a reaction time of a further two hours, a water pump vacuum was applied for one hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large quantity of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
139 parts of water and 2 parts of polyvinylpyrrolidone K 90 as a 5% strength solution in water (a product from GAF) were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser, metering device and nitrogen flushing device, and the mixture was heated to 70° C., while flushing with nitrogen. When the temperature had been reached, the following meterings were carried out rapidly, while stirring vigorously and flushing with nitrogen: Metering 1: a mixture of 49 parts of vinyl acetate, 50 parts of VeoVa 9, 1 part of citraconic anhydride, 0.1 part of tert-butyl peroxypivalate and 0.05 part of dibenzoyl peroxide. Metering 2: 6 parts of water and 0.1 part of bis(2-ethylhexyl) peroxodicarbonate. After a reaction time of 4 hours, the temperature was increased to 80° C., and after a reaction time of a further two hours, a water pump vacuum was applied for one hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large quantity of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
49 parts of vinyl acetate, 50 parts of VeoVa 9, 1 part of maleic anhydride, 0.1 part of bis(2-ethylhexyl) peroxodicarbonate, 0.1 part of tert-butyl peroxypivalate and 0.3 part of dibenzoyl peroxide were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser and nitrogen flushing device, and the mixture was diluted with ethyl acetate to the extent that a 40% strength solution was formed. The solution was then heated, while flushing vigorously with nitrogen, and kept under reflux for 20 hours. Thereafter, a water pump vacuum was applied for 2 hours and the mixture was cooled to room temperature. The solids content was adjusted to 20% with ethyl acetate.
49 parts of vinyl acetate, 50 parts of VeoVa 9, 1 part of crotonic acid and 0.02 part of tert-butyl peroxypivalate were initially introduced into a polymerization vessel with an anchor stirrer, reflux condenser, metering device and nitrogen flushing device, and the mixture was diluted with ethyl acetate such that a 60% strength solution was formed. The solution was then heated to 70° C., while flushing vigorously with nitrogen. After the exothermic reaction had started, 0.03 part of tert-butyl peroxypivalate in 10 parts of ethyl acetate were added over a period of 2 hours. After a reaction time of 4 hours, a water pump vacuum was applied at 70° C. for one hour. After cooling to room temperature, the polymer solution was precipitated in 10 times the amount of petroleum ether, the precipitate was filtered off with suction and dried and a 20% strength solution of the polymer in ethyl acetate was prepared.
44 parts of vinyl acetate, 45 parts of VeoVa 9, 1 part of maleic anhydride, 10 parts of tert-butyl acrylate, 0.05 part of bis(2-ethylhexyl) peroxodicarbonate, 0.05 part of tert-butyl peroxypivalate, 0.025 part of dibenzoyl peroxide and 2 parts of polyvinylpyrrolidone K 90 as a 5% strength aqueous solution (product from GAF) were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser and nitrogen flushing device, and water was added, while stirring, in an amount such that the content of monomers was 35 percent by weight. The mixture was heated to 70° C., while flushing vigorously with nitrogen. After a reaction time of 6 hours, a water pump vacuum was applied at a temperature of 80° C. for one hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large amount of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
176 parts of water and 0.5 part of Eballoid, dissolved in 8.6 parts of water (Eballoid is a polyvinyl ester containing carboxyl groups, a product from Wacker Chemie GmbH), were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser, metering device and nitrogen flushing device, and the mixture was heated to 70° C., while flushing with nitrogen. When the temperature had been reached, the following meterings were carried out rapidly, while stirring vigorously and flushing with nitrogen: Metering 1: a mixture of 44 parts of vinyl acetate, 49 parts of VeoVa 9, 1 part of maleic anhydride, 10 parts of N-vinylpyrrolidone, 0.05 part of tert-butyl peroxypivalate and 0.025 part of dibenzoyl peroxide. Metering 2: 6 parts of water and 0.05 part of bis(2-ethylhexyl) peroxodicarbonate. After a reaction time of 4 hours, the temperature was increased to 80° C., and after a reaction time of one hour, a water pump vacuum was applied for half an hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large amount of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
96.9 parts of water and 2 parts of Tylose H 4000 (a product from Hoechst) were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser, metering device and nitrogen flushing device, and the mixture was heated to 70° C., while flushing with nitrogen. When the Tylose had dissolved, the following meterings were carried out rapidly, while stirring vigorously and flushing with nitrogen: Metering 1: a mixture of 42 parts of vinyl acetate, 42 parts of VeoVa 9, 1 part of maleic anhydride, 15 parts of tertbutyl acrylate, 0.1 part of tert-butyl peroxypivalate and 0.05 part of dibenzoyl peroxide. Metering 2: 6 parts of water and 0.1 part of bis-(2ethylhexyl) peroxodicarbonate. After a reaction time of 2 hours, the temperature was increased to 80° C., and after a reaction time of one hour, a water pump vacuum was applied for half an hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large amount of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
146 parts of water and 2 parts of polyvinylpyrrolidone K 90 as a 5% strength solution in water (a product from GAF) were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser, motoring device and nitrogen flushing device, and the mixture was heated to 70° C., while flushing with nitrogen. When the temperature had been reached, the following meterings were carried out rapidly, while stirring vigorously and flushing with nitrogen: Metering 1: a mixture of 49 parts of vinyl acetate, 50 parts of VeoVa 9, 1 part of maleic anhydride, 0.05 part of tert-butyl peroxypivalate and 0.025 part of dibenzoyl peroxide. Metering 2: 6 parts of water and 0.05 part of bis(2-ethylhexyl) peroxodicarbonate. After a reaction time of 6 hours, the temperature was increased to 80° C., and after a reaction time of one hour, a water pump vacuum was applied for half an hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large amount of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
149 parts of water were initially introduced into a polymerization vessel with an anchor stirrer, reflux condenser, metering device and nitrogen flushing device, and were heated to 70° C., while flushing with nitrogen. When the temperature had been reached, the following meterings were carried out rapidly, while stirring vigorously and flushing with nitrogen: Motoring 1: a mixture of 49 parts of vinyl acetate, 50 parts of VeoVa 9, 1 part of maleic anhydride, 0.05 part of tert-butyl peroxypivalate and 0,025 part of dibenzoyl peroxide. Metering 2:6 parts of water and 0.05 part of bis(2-ethylhexyl) peroxodicarbonate. 35 minutes after the exothermic reaction had started, 2 parts of Eballoid as a 5.5% strength aqueous solution were added rapidly. After a reaction time of 6 hours, the temperature was increased to 80° C., and after a further hour, a water pump vacuum was applied for half an hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large amount of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
142 parts of water and 2 parts of polyvinylpyrrolidone K 90 as a 5% strength aqueous solution containing 2% of copper acetate were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser, metering device and nitrogen flushing device, and the mixture was heated to 70° C., while flushing with nitrogen. When the temperature had been reached, the following meterings were carried out rapidly, while stirring vigorously and flushing with nitrogen: Metering 1: a mixture of 49 parts of vinyl acetate, 50 parts of VeoVa 9, 1 part of maleic anhydride, 0.1 part of tert-butyl peroxypivalate and 0.05 part of dibenzoyl peroxide. Metering 2: 6 parts of water and 0.1 part of bis(2-ethylhexyl) peroxodicarbonate. After a reaction time of 6 hours, the temperature was increased to 80° C., and after a further hour, a water pump vacuum was applied for half an hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large amount of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
189 parts of water and 2 parts of polyvinylpyrrolidone K 90 as a 5% strength aqueous solution were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser, metering device and nitrogen flushing device, and the mixture was heated to 70° C., while flushing with nitrogen. When the temperature had been reached, the following meterings were carried out rapidly, while stirring vigorously and flushing with nitrogen: Metering 1: a mixture of 65 parts of vinyl acetate, 34 parts of dimethyl maleate, 1 part of maleic anhydride, 0.1 part of tert-butyl peroxypivalate and 0.15 part of dibenzoyl peroxide. Metering 2: 6 parts of water and 0.1 part of bis(2-ethylhexyl) peroxodicarbonate. After a reaction time of 6 hours, the temperature was increased to 80° C., and after a further hour, a water pump vacuum was applied for half an hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large amount of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
189 parts of water and 2 parts of polyvinylpyrrolidone K 90 as a 5% strength aqueous solution were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser, metering device and nitrogen flushing device, and the mixture was heated to 70° C., while flushing with nitrogen. When the temperature had been reached, the following meterings were carried out rapidly, while stirring vigorously and flushing with nitrogen: Metering 1: a mixture of 69 parts of vinyl acetate, 30 parts of diisopropyl fumarate, 1 part of maleic anhydride, 0.1 part of tert-butyl peroxypivalate and 0.15 part of dibenzoyl peroxide. Metering 2:6 parts of water and 0.1 part of bis(2-ethylhexyl) peroxodicarbonate. After a reaction time of 6 hours, the temperature was increased to 80° C., and after a further hour, a water pump vacuum was applied for half an hour. After cooling to room temperature the resulting beads were filtered off with suction and washed with a large amount of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
189 parts of water and 2 parts of polyvinylpyrrolidone K 90 as a 5% strength aqueous solution were initially introduced into a polymerization vessel with a paddle stirrer, reflux condenser, metering device and nitrogen flushing device, and the mixture was heated to 70° C., while flushing with nitrogen. When the temperature had been reached, the following meterings were carried out rapidly, while stirring vigorously and flushing with nitrogen: Metering 1: a mixture of 65 parts of vinyl acetate, 34 parts of 4-tert-butylcyclohexyl acrylate, 1 part of maleic anhydride, 0.1 part of tert-butyl peroxypivalate and 0.15 part of dibenzoyl peroxide. Metering 2: 6 parts of water and 0.1 part of bis(2-ethylhexyl) peroxodicarbonate. After a reaction time of 6 hours, the temperature was increased to 80° C., and after a further hour, a water pump vacuum was applied for half an hour. After cooling to room temperature, the resulting beads were filtered off with suction and washed with a large amount of water. A 20% strength solution of the dry polymer in ethyl acetate was prepared.
Use technology testing:
The vinyl ester copolymers from Examples 1 to 20 and films thereof on aluminum foil were tested by the methods described below:
Determination of the K value:
The K values were determined in tetrahydrofuran in accordance with H. Fikentscher, Cellulosechemie 13, 58-64 (1932).
Determination of the glass transition temperatures Tg :
The glass transition temperatures were determined by means of DSC measurements using an apparatus from Perkin Elmer, the middle point of the glass stage being taken as the glass transition temperature and the heating rate being in each case 20° C./minute.
Determination of the chalking:
To test the chalking, a glass plate was coated with a 250 μm wet film (solids content of the solution 20%) and dried at 120° C. for 20 minutes. It was then stored in water for 5 hours. The chalking was determined visually in accordance with the following scale of ratings:
1=The film shows no chalking.
2=The film shows a slight white haze.
3=The film is slightly white.
4=The film is white.
Determination of the adhesive strength on aluminum foil:
To test the adhesion of the polymer film to an aluminum foil, the foil was first cleaned with ethanol and then coated with a 50 μm wet film (20%) and dried at 120° C. for 20 minutes. A strip of tesafilm adhesive tape was pressed onto this polymer film with firm finger pressure. The adhesive strip was in one case torn off again immediately; the second test was carried out after the coated aluminum foil had been stored in water at room temperature for 24 hours. The film was then wiped dry with a cloth and the tesa strip was stuck on with firm finger pressure and immediately torn off again. The third test was carried out after the coated aluminum foil had been stored in water for 24 hours and then stored at room temperature for 24 hours. Thereafter, the adhesive strip was fixed with firm finger pressure and immediately torn off again. The adhesive strength was evaluated visually in accordance with the following scale of ratings:
1=Good adhesion of the polymer film; no peeling of the coating was found at all.
2=Isolated areas of the polymer film were removed.
3=Several areas of the polymer film were removed.
4=The polymer film shows no adhesion to the aluminum foil and the coating was detached completely.
Determination of the block point:
To determine the block point, the aluminum foil was coated with a 50 μm wet film (20% strength) and dried at 120° C. for 20 minutes. Thereafter, the aluminum foil was folded so that the coated areas lay on top of one another. Testing was carried out in a sealing unit at various temperatures to ascertain whether the polymer films stick together, the sealing time being 30 seconds and the pressing pressure 2.5 Kp/cm2. The temperature in °C. at which the aluminum foil can no longer be separated without applying force, that is to say the polymer film became tacky, was stated as the block point or block temperature.
Determination of the sealing seam strength (SSS):
The sealing seam strength was determined by the following method: an aluminum foil coated with a 50 μm wet film (20% strength) and dried at 120° C. for 20 minutes was folded together so that the sides coated with the polymer lay on top of one another. The foil was sealed with a sealing unit at a temperature of 190° C. for 0.5 second under a pressing pressure of 10 Kp/cm2. The sealing area was 4×1 cm. The force required to peel the aluminum foil apart again at room temperature was then measured on a unit from Instron. The measurement was carried out both in the dry and in the wet state. For the determination of the SSS in the wet state, the coated and sealed aluminum foil was first stored in water at room temperature for 24 hours and then examined immediately as described above.
In Table 1:
Aluminum adhesion:
1st value=adhesion in the dry state;
2nd value=adhesion after storage in water at room temperature for 24 hours;
3rd value=adhesion after storage in water for 24 hours and storage at room temperature for 24 hours
TABLE 1 __________________________________________________________________________ Block point Aluminum SSS (N/cm) SSS (N/cm) Example K value T.sub.g (°C.) (°C.) Chalking adhesion dry wet __________________________________________________________________________ 1 37.4 37 55 1 1/1/1 0.88 0.84 2 86.3 60 1 1/4/4 0.82 0.24 3 45.8 39 50 1 1/1-2/1 2.19 1.97 4 73.1 36 55 1 1/1-2/1 2.03 1.76 5 46.6 42 55 1 1/1/1 2.51 2.37 6 71.1 44 50 1 1/1/1 2.13 1.46 7 64.2 45 55 1 1/1/1 2.70 2.50 8 55.1 34 50 1 1/1/1 1.38 1.13 9 57.3 38 55 1 1/1/1 1.08 1.12 10 32.4 40 50 1 1/1/1 0.63 0.52 11 41.6 25 65 1 1/3/2 1.00 1.00 12 65.3 35 55 1 1/1-2/1 2.13 1.49 13 26.9 36 50 1 1/1/1 2.06 1.53 14 58.1 34 50 1 1/1/1 1.63 1.46 15 64.4 35 55 1 1/1/1 2.12 1.70 16 43.5 36 50 1 1/1/1 2.86 2.18 17 77.1 39 50 1 1/1/1 2.04 1.48 18 37.4 62 70 1 1/1-2/1 1.07 0.91 19 58.6 44 65 1 1/1/1 2.63 2.52 20 70.1 32 80 1 1/4/1 0.82 0.63 __________________________________________________________________________
Claims (9)
1. A heat sealable coating agent composition for coating aluminum consisting of a vinyl ester copolymer and an organic solvent, the vinyl ester copolymer being free of chlorine-containing polymers, having a glass transition temperature Tg of 20° to 100° C., a block point in the range from 30° to 150° C. and a K value of 25 to 120 and comprising:
(a) 20 to 90 parts by weight of a vinyl ester of saturated aliphatic monocarboxylic acids having 1 to 5 C atoms,
(b) 0 to 70 parts by weight of a vinyl ester of saturated aliphatic monocarboxylic acids having 9 to 10 C atoms and a quaternary C atom in the G-position relative to the carboxyl group,
(c) 0.05 to 10 parts by weight of at least one ethylenically unsaturated dicarboxylic acid having 3 to 10 C atoms or anhydrides thereof and
(d) 0 to 50 parts by weight of at least one ethylenically unsaturated monomer, the homopolymers having a glass transition temperature above 30° C., all of said parts by weight being based on the total weight of said copolymer.
2. A coating agent composition as claimed in claim 1, wherein the vinyl ester copolymer has a glass transition temperature Tg of 20° to 100° C., a block point in the range from 30° to 150° C. and a K value of 25 to 120 and comprises
a) 25 to 85 parts by weight of vinyl acetate,
b) 0 to 55 parts by weight of vinyl ester of an alpha-branched saturated mono carboxylic acid containing 9 carbon atoms,
c) 0.5 to 5 parts by weight of at least one comonomer selected from the group consisting of maleic acid, fumaric acid, itaconic acid, maleic anhydride, allylsuccinic anhydride, mesaconic acid, citraconic acid and citraconic anhydride, and
d) 0 to 40 parts by weight of at least one comonomer selected from the group consisting of methyl methacrylate, tertbutyl acrylate, N-vinylpyrrolidone, N-vinylcarbazole, dimethyl maleate, diisopropyl maleate, diisopropyl fumarate, di-tert-butyl maleate, di-tert-butyl fumarate and 4-tert-butylcyclohexyl acrylate.
3. A coating agent composition as claimed in claim 1 or 2, wherein the vinyl ester copolymer has a glass transition temperature Tg of 30° to 70° C., a block point in the range from 45° to 100° C. and a K value of 30 to 80 and comprises
a) 40 to 50 parts by weight of vinyl acetate,
b) 40 to 50 parts by weight of vinyl ester of an alpha-branched saturated mono carboxylic acid containing 9 carbon atoms,
c) 0.5 to 3 parts by weight of at least one comonomer selected from the group consisting of maleic acid, fumaric acid, itaconic acid and maleic anhydride, and
d) 5 to 20 parts by weight of at least one comonomer selected from the group consisting of methyl methacrylate, tertbutyl acrylate, N-vinylpyrrolidone, N-vinylcarbazole, dimethyl maleate, diisopropyl maleate, diisopropyl fumarate, di-tert-butyl maleate, di-tert-butyl fumarate and 4-tert-butylcyclohexyl acrylate.
4. A coating agent composition as claimed in claim 1 or 2, wherein the vinyl ester copolymer has a glass transition temperature Tg of 30° to 70° C., a block point in the range from 45° to 100° C. and a K value of 30 to 80 and comprises
a) 45 to 55 parts by weight of vinyl acetate,
b) 45 to 55 parts by weight of vinyl ester of alpha-branched saturated mono carboxylic acid containing 9 carbon atoms and
c) 0.5 to 3 parts by weight of at least one comonomer selected from the group consisting of maleic acid, fumaric acid, itaconic acid and maleic anhydride.
5. A coating agent composition as claimed in claim 1 or 2, wherein the vinyl ester copolymer has a glass transition temperature Tg of 30° to 70° C., a block point in the range from 45° to 100° C. and a K value of 30 to 80 and comprises
a) 60 to 85 parts by weight of vinyl acetate,
c) 0.5 to 3 parts by weight of at least one comonomer selected from the group consisting of maleic acid, fumaric acid, itaconic acid and maleic anhydride and
d) 15 to 40 parts by weight of at least one comonomer selected from the group consisting of methyl methacrylate, tertbutyl acrylate, N-vinylpyrrolidone, N-vinylcarbazole, dimethyl maleate, diisopropyl maleate, diisopropyl fumarate, di-tert-butyl maleate, di-tert-butyl fumarate and 4-tert-butylcyclohexyl acrylate.
6. A coating agent composition as claimed in claim 5, wherein the vinyl ester copolymer has a glass transition temperature Tg of 30 to 70° C., a block point in the range from 45° to 100° C. and a K value of 30 to 80 and comprises
a) 60 to 85 parts by weight of vinyl acetate,
c) 0.5 to 3 parts by weight of at least one member selected from the group consisting of fumaric acid and maleic anhydride and
d) 15 to 40 parts by weight of at least one comonomer selected from the group consisting of dimethyl maleate, diisopropyl maleate, diisopropyl fumarate and di-tert-butylcyclohexyl acrylate.
7. A coating agent composition as claimed in claim 1, wherein the vinyl ester copolymer is prepared by a suspension polymerization process.
8. A coating agent composition as claimed in claim 1, wherein carboxylic acid esters, ketones, alcohols or ethers are used as the organic solvent to form a solution and the solids content of the solution is from 10 to 70% by weight.
9. A coating agent composition of claim 1 wherein the vinyl ester copolymer consists of
a) 60 to 85 parts by weight of vinyl acetate,
c) 0.5 to 3 parts by weight of at least one member selected from the group consisting of fumaric acid and maleic anhydride and
d) 15 to 40 parts by weight of at least one comonomer selected from the group consisting of dimethyl maleate, diisopropyl maleate, diisopropyl fumarate, di-tert-butyl maleate and di-tert-butyl fumarate.
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US7271293A | 1993-06-07 | 1993-06-07 | |
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JPS57165471A (en) * | 1981-04-06 | 1982-10-12 | Daicel Chem Ind Ltd | Adhesive for laminating paper and aluminum foil |
JPS57165472A (en) * | 1981-04-06 | 1982-10-12 | Daicel Chem Ind Ltd | Adhesive for laminating paper and aluminum foil |
JPS6017437B2 (en) * | 1981-04-07 | 1985-05-02 | ダイセル化学工業株式会社 | Adhesive for paper-aluminum foil lamination |
JPS5984956A (en) * | 1982-11-05 | 1984-05-16 | Nippon Paint Co Ltd | Resin composition for antifouling coating compound |
JPS59124970A (en) * | 1983-01-04 | 1984-07-19 | Daicel Chem Ind Ltd | Adhesive for aluminum foil |
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1992
- 1992-06-05 DE DE4218663A patent/DE4218663A1/en not_active Withdrawn
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1993
- 1993-06-03 EP EP93108935A patent/EP0573037B1/en not_active Expired - Lifetime
- 1993-06-03 ES ES93108935T patent/ES2100392T3/en not_active Expired - Lifetime
- 1993-06-03 JP JP5156333A patent/JP2973386B2/en not_active Expired - Lifetime
- 1993-06-03 DE DE59305515T patent/DE59305515D1/en not_active Expired - Fee Related
- 1993-06-03 AT AT93108935T patent/ATE149187T1/en not_active IP Right Cessation
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- 1994-08-03 US US08/285,770 patent/US5525656A/en not_active Expired - Lifetime
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5880239A (en) * | 1995-06-08 | 1999-03-09 | Wacker-Chemie Gmbh | Fusible chlorine-free vinyl acetate copolymer fibres |
US6201685B1 (en) | 1998-10-05 | 2001-03-13 | General Electric Company | Ultracapacitor current collector |
US6565701B1 (en) | 1998-10-05 | 2003-05-20 | General Electric Corporation | Ultracapacitor current collector |
US20060069194A1 (en) * | 2004-09-21 | 2006-03-30 | Wolfgang Stauf | Low-emission adhesive composition based on a solvent |
US7420009B2 (en) * | 2004-09-21 | 2008-09-02 | Stauf Klebstoffwerk Gmbh | Low-emission adhesive composition based on a solvent |
CN103403046A (en) * | 2011-02-22 | 2013-11-20 | 迈图专业化学股份有限公司 | Elastomeric polymer compositions for coatings and sealants |
US9404008B2 (en) | 2011-02-22 | 2016-08-02 | Hexion Inc. | Elastomeric polymer compositions for coatings and sealants |
CN103403046B (en) * | 2011-02-22 | 2016-10-19 | 瀚森公司 | For coating and the elastomeric polymer composition of sealant |
US10800867B2 (en) | 2012-12-05 | 2020-10-13 | Hexion Inc. | Process to produce polyvinyl-ester compositions with low residual monomer and the use thereof |
Also Published As
Publication number | Publication date |
---|---|
JP2973386B2 (en) | 1999-11-08 |
ATE149187T1 (en) | 1997-03-15 |
ES2100392T3 (en) | 1997-06-16 |
JPH0633011A (en) | 1994-02-08 |
EP0573037A1 (en) | 1993-12-08 |
DE59305515D1 (en) | 1997-04-03 |
EP0573037B1 (en) | 1997-02-26 |
DE4218663A1 (en) | 1993-12-09 |
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